Fast recovery soft thermoplastic polyurethanes

Abstract

The thermoplastic polyurethane compositions described herein have very good recovery properties, rebound resilience, or both, while also having good softness (i.e. low hardness). It has been difficult to provide thermoplastic polyurethane compositions with this combination of properties. Some compositions described herein also provide low haze and/or good clarity properties. These combination of properties make the thermoplastic polyurethane compositions described herein useful materials for application that require fast recovery, good rebound resilience, or both while also requiring soft materials, and in some embodiments low haze and/or good clarity.

1 . A molded article comprising:
 a thermoplastic polyurethane composition formed from reaction product of:
 a) a polyisocyanate; 
 b) a polyol component comprising at least one polycaprolactone polyester polyol; and 
 c) a chain extender component comprising at least one diol chain extender of the general formula HO—(CH 2 ) x —OH wherein x is an integer from 9 to about 16. 
 wherein the thermoplastic polyurethane composition has a Shore D hardness of less than 60, a haze value of less than 36, and a DMA value measured at 0.1 rad/s of less than 0.1880, and a DMA value measure at 100 rad/s of less than 0.2660. 
   
     
     
         2 . (canceled) 
     
     
         3 . (canceled) 
     
     
         4 . (canceled) 
     
     
         5 . The article of  claim 1 , wherein the polycaprolactone polyester polyol has a number average molecular weight from 2000 to 3000. 
     
     
         6 . The article of  claim 1 , wherein the chain extender component comprises 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, or a combination thereof 
     
     
         7 . (canceled) 
     
     
         8 . (canceled) 
     
     
         9 . (canceled) 
     
     
         10 . (canceled) 
     
     
         11 . A process of making an article, comprising:
 providing a thermoplastic polyurethane composition made from the reaction of:
 a) a polyisocyanate; 
 b) a polyol component comprising at least one polycaprolactone polyester polyol; and 
 c) a chain extender component comprising at least one diol chain extender of the general formula HO—(CH 2 ) x —OH wherein x is an integer from 9 to about 16; 
 wherein the thermoplastic polyurethane composition has a Shore D hardness of less than 60, a haze value of less than 36, and a DMA value meausred at 0.1 rad/s of less than 0.1880, and a DMA value measure at 100 rad/s of less than 0.2660; 
 and molding said thermoplastic polyurethane composition to form an article. 
   
     
     
         12 . (canceled) 
     
     
         13 . (cancelled) 
     
     
         14 . (canceled) 
     
     
         15 . The article of  claim 5 , wherein the chain extender is 1,12-dodecanediol. 
     
     
         16 . The article of  claim 1 , wherein the polyisocyanate and chain extender make up a hard segment of the thermoplastic polyurethane composition and wherein the thermoplastic polyurethane composition comprises 44.5 to 66 weight percent hard segment. 
     
     
         17 . The article of  claim 16 , wherein the molar ratio of the chain extender to the polyol of the thermoplastic polyurethane composition is from 2.93:1 to 7.89:1. 
     
     
         18 . The process of  claim 11 , wherein the polycaprolactone polyester polyol has a number average molecular weight from 2000 to 3000. 
     
     
         19 . The process of  claim 18 , wherein the chain extender is 1,12-dodecanediol. 
     
     
         20 . The process of  claim 11 , wherein the polyisocyanate and chain extender make up a hard segment of the thermoplastic polyurethane composition and wherein the thermoplastic polyurethane composition comprises 44.5 to 66 weight percent hard segment. 
     
     
         21 . The process of  claim 20 , wherein the molar ratio of the chain extender to the polyol of the thermoplastic polyurethane composition is from 2.93:1 to 7.89:1.